CN1308570A

CN1308570A - Coated abrasive article

Info

Publication number: CN1308570A
Application number: CN99808171A
Authority: CN
Inventors: R·J·德沃; T·M·克劳森; G·D·达尔克; C·A·乔治; N·卡里姆; C·A·马斯马
Original assignee: Minnesota Mining and Manufacturing Co
Current assignee: 3M Co
Priority date: 1998-05-01
Filing date: 1999-03-05
Publication date: 2001-08-15
Anticipated expiration: 2019-03-05
Also published as: CA2330853A1; DE69922945D1; EP1075354A1; WO1999056913A1; DE69922945T2; US6359027B1; CN1139461C; JP2002513684A; KR20010043184A; BR9910108A; EP1075354B1; US6372336B1; US6077601A; US6258138B1

Abstract

A coated abrasive article comprises a backing, a first binder on the backing, and a plurality of abrasive particles in the first binder. The first binder precursor is an energy-curable preferably, melt-processable resin containing an epoxy resin, an ethylene-vinyl acetate copolymer, and a curing agent for crosslinking the epoxy resin that is cured to provide a crosslinked make coating. The above binder precursors of the invention are preferably free of homopolymers and copolymers of olefinic monomers. In another aspect, the invention also describes an energy curable first binder precursor containing an epoxy resin, an ethylene-vinyl acetate copolymer, a polyfunctional acrylate component and a curing agent for crosslinking the epoxy resin that is cured to provide a crosslinked make coating. The invention also relates to a method of producing such coated abrasive articles and a surface-treated backing material.

Description

Coated abrasive article

The present invention relates to coated abrasive article, but relate more specifically to comprise the coated abrasive article of energy curing composition.But above-mentioned energy curing composition contains Resins, epoxy and vinyl-vinyl acetate copolymer or Resins, epoxy, vinyl-vinyl acetate copolymer and acrylate.

Coated abrasive generally comprises a flexible backing, the binding agent on the backing (binder) supporting abrasive coating.Abrasive particle generally is fixed on the backing with first binding agent (being commonly referred to initial adhesive coating (make coat)).In order to obtain best grinding rate, abrasive particle generally is orientated in the mode of its longest dimension perpendicular to backing in addition.Then second binding agent (being commonly referred to sizing menting property (size coat)) is applied on initial adhesive coating and the abrasive particle, so that abrasive particle is fixed on the backing.

Porous cloth, fabric and textile material usually are used as the backing of coated abrasive article.Initial adhesive coating precursor generally with low viscous coated materials to backing.Under this condition, initial adhesive coating precursor may be penetrated in the space of porous backing, makes coat-thickness not enough, thereby is difficult to the abrasive particle of coating subsequently is bonded on the backing.And when solidifying, backing is anchylosed and become fragile.Therefore, use one or more to handle coating usually,, come sealing porous backing as pre-sizing menting property (presize coat), saturated coating, gum knot coating (backsize coat) or primer knot coating (subsize coat).

Pre-sizing menting property, saturated coating, gum knot coating and primer knot coating generally comprise the resin glue of thermofixation, as resol, Resins, epoxy, acrylate resin, acrylic latex, urethane resin, cementing agent, starch and composition thereof.Saturated coating makes the saturated and filling space of cloth, thereby produces the cloth that the space is less and stiffness reduces, and has increased the body of cloth.The increase of body has improved the intensity and the weather resistance of goods.The pre-sizing menting property that is coated in the backing front surface can increase the volume of cloth, and improves the binding property of coating later on.The gum knot coating that is coated in the backing rear surface surface of surface opposite of coating abrasive particle (promptly with) has increased the yarn protected from wear of the body and the protecting cloth of backing.Primer knot coating is similar to saturated coating, and different is that it is coated on the pretreated backing.The shortcoming of these pre-sizing menting properties, saturated coating, gum knot coating and primer knot coating is to need additional treatment step, has increased manufacturing cost and complexity.Equally, but also treatment paper backing, to prevent glued adhesive penetration and/or to make it have water-repellancy.

The invention provides a kind of coated abrasive article.It comprises:

A) has the backing of front surface and rear surface;

B) crosslinked first binding agent on described backing front surface, described first binding agent is made by first binder precursor, but described first binder precursor is by mixing the energy cured compositions that following component makes:

I) total content that about 2-99% weight ring epoxy resins, weight percentage are pressed resin calculates;

The total content that ii) about 1-98% weight ethylene-vinyl acetate copolymer resin, weight percentage are pressed resin calculates;

Iii) significant quantity is used for crosslinked described curing agent for epoxy resin; With

C) many abrasive particles, described abrasive particle to small part are embedded in described first binding agent.

Above-mentioned binder precursor composition of the present invention is a homogeneous under molten state, better hydrocarbon-containifirst polyolefin resin not." hydro carbons polyolefin resin " is meant the uncrosslinked polymeric hydrocarbon of the complete pre-polymerization that is substantially free of organic functional group that is made by the homopolymerization of olefinic monomer and/or copolymerization.These resins can be incompatible with Resins, epoxy, and the composition that contains significant quantity Resins, epoxy is separated.The example of these resins comprises polyethylene, polypropylene etc. and ethylene-propylene copolymer, propylene-butene-1 copolymer etc.

Another aspect of the present invention provides a kind of coated abrasive article.It comprises:

A) has the backing of front surface and rear surface;

I) total content that about 2-98% weight ring epoxy resins, weight percentage are pressed resin calculates;

The total content that ii) about 1-90% weight ethylene-vinyl acetate copolymer resin, weight percentage are pressed resin calculates;

The total content that iii) about 0.1-20% weight polyfunctional acrylic ester, weight percentage are pressed resin calculates; With

Iv) significant quantity is used for crosslinked described curing agent for epoxy resin; With

But it is a kind of by mixing the energy cured compositions that following component is made that a third aspect of the present invention provides:

A) Resins, epoxy;

B) ethylene-vinyl acetate copolymer resin;

C) polyfunctional acrylic ester;

D) solidifying agent that is used for cross-linked epoxy resin of significant quantity.

A fourth aspect of the present invention is provided for the pre-glued backing of coated abrasive article.It comprises:

A) be applicable to the backing of coated abrasive article; With

B) the crosslinked pre-glued layer that forms by pre-glued binder precursor on the described backing, but described pre-glued binder precursor is the energy cured compositions that contains following component:

I) total content that about 30-95% weight ring epoxy resins, weight percentage are pressed resin calculates;

The total content that ii) about 5-70% weight ethylene-vinyl acetate copolymer resin, weight percentage are pressed resin calculates;

Iii) significant quantity is used for crosslinked described curing agent for epoxy resin.

A fifth aspect of the present invention provides a kind of pre-glued backing that is used for coated abrasive article.It comprises:

A) be applicable to the backing of coated abrasive article; With

The total content that iii) about 0.1-20% weight polyfunctional acrylic ester component, weight percentage are pressed resin calculates; With

Iv) significant quantity is used for crosslinked described curing agent for epoxy resin.

A sixth aspect of the present invention provides a kind of method for preparing coated abrasive article.It comprises the steps:

(a) provide backing with front surface and rear surface;

(b) but on the front surface of described backing first binder precursor of coating energy solidified, melt-processable, described first binder precursor comprises:

I) Resins, epoxy;

Ii) ethane-acetic acid ethyenyl ester; With

Iii) be used for crosslinked described curing agent for epoxy resin;

(c) described first binder precursor is placed under the energy, to cause the partly solidified at least of described first binder precursor;

(d) many abrasive particles to small part is imbedded in described first binder precursor; With

(e) described first binder precursor is fully solidified, form described abrasive particle to small part and imbed wherein cross-linked coating.

Above-mentioned binder precursor of the present invention better is a melt-processable.

Used " hot melts " is meant and a kind ofly is being solid under the room temperature (about 20-22 ℃) but the time is fused into the composition that is easy to be applied to the viscous liquid on the coated abrasive article backing in heating among the application." melt-processable " composition for example is meant depresses the composition that is converted into viscous liquid by the solid fusion through heating and/or adding, and at this moment it can be easy to be applied on the coated abrasive article backing.The solid film form that the resin combination of hot melt and melt-processed can be a transfer coating to the backing.Hot-melt composition of the present invention should be mixed with solvent-free system (solvent is lower than 1% when being solid-state).

Yet if necessary, also can in binder precursor, add solvent or other volatile matter.The hot-melt composition that shows pressure-sensitive-adhesive when used " pressure sensitive adhesive " is meant the coating abrasive particle among the application." pressure-sensitive-adhesive " be meant and just be coated on the backing and when still warm, and composition has viscosity sometimes even behind cool to room temperature." EVA " is meant vinyl-vinyl acetate copolymer, and " epoxy (epoxy) " is meant the material or the Resins, epoxy that contain epoxide.

In yet another embodiment of the present invention, in order to strengthen the bonding of abrasive particle and backing, can on initial adhesive coating and abrasive particle, be coated with sizing menting property (i.e. second binding agent).Also sizing menting property can used on the sizing menting property, i.e. the 3rd binding agent.

Before the coating, initial adhesive coating precursor or binder precursor can be solids, and can be coated with liquor or molten mixture.

But the invention still further relates to pressure-sensitive first binding agent of energy solidified hot melt is handled coating as the backing of porous fabrics, for example as the saturated coating of protecting cloth fiber and/or sealing porous cloth, pre-sizing menting property, gum knot coating or primer knot coating.If liquefaction, binder precursor can be coated with into sizing menting property.More fortunately on the treat surface of backing before coating precursor and the abrasive particle, but will be coated on that any backing treatment agent (as pre-jointing compound) on the coating surface of backing solidifies or crosslinked.The coating or the treatment agent that are solidificated on the backing better are substantially free of abrasive particle.

Binder precursor of the present invention generally also has the unlimited time longer than the initial engagement coating resin of polyester/epoxies melt-processable (open time), better film forming properties (can make) and lower cost under lower content.Binder precursor of the present invention also has significant viscosity under its uncured state, controllable flowability is arranged in solidification process and have required physicals under the state after the curing, comprises bond strength and cohesive strength.

Fig. 1 is the amplification view of part coated abrasive article in one embodiment of the present invention.

Referring now to accompanying drawing,, Fig. 1 represents coated abrasive article 10 of the present invention, and it comprises backing 12 and the abrasive material 14 that is bonded on the backing.

Backing 12 can be the coated abrasive article or the porous unsealing backing of conventional sealing.Backing 12 can be cloth, vulcanised fibre, paper, nonwoven material, fibre-reinforced thermoplastic backing, the substrate that contains hooked rod, round fabric, tinsel, reticulated, foam-back and their laminated multilayer matrix material.

The cloth backing can be untreated, the backing of saturated, pre-gluing, gum knot, porous or sealing, these backings can be weaved or sew up with pin.The cloth backing can comprise the fiber or the yarn of cotton, polyester, artificial silk, silk, nylon or its mixture.The cloth backing can be made the laminated product of above-mentioned different back lining materials.

The paper backing also can be tied, be untreated or fiber reinforcement by saturated, antiseepage coating, pre-gluing, gum.The paper backing also can be made into the laminated product of dissimilar back lining materials.Non-woven backing comprises the scrim (scrim) and the laminating material of above-mentioned different back lining materials.Non-woven backing also can be made by cellulosic fibre, synthon or its mixture.This backing also can be separately or the shaft-like sheet stock (stemweb) that uses in conjunction with supatex fabric or with the laminating material of dissimilar backings.

The round fabric liner can be napping nylon, napping polyester, the knitting round fabric of polyester and be laminated to round material on the different backings.Foam-back can be natural sponge material or polyurethane foamed material etc.

Foam-back also can be laminated on the dissimilar back lining materials.The reticulated backing can be made by polymkeric substance or the rare scrim of knitting of metal.In addition, backing can be as at United States Patent (USP) 5,573, the enhancing thermoplasticity backing that discloses in endless belt that discloses in 619,5,609,706 and 5,681,612 or the United States Patent (USP) 5,417,726.

Abrasive material 14 comprises with first binding agent (being initial adhesive coating) 18 and is bonded to a large amount of abrasive particles 16 on backing 12 major surfacess.Second binding agent (being sizing menting property) 20 is coated on abrasive particle and the initial adhesive coating, to reinforce abrasive particle.The mean diameter of these abrasive particles generally is about 0.1-1500 micron (μ m), better is about the 1-1300 micron.The example of useful abrasive particle comprises the fused alumina sill, coagulates aluminium-zirconium oxide, diamond, cerium oxide, TiB2, cubic boron nitride, norbide, garnet and their mixture as aluminum oxide, ceramic alumina (can contain one or more metal oxide modified agent and/or crystal seed agent or nucleator) and heat treated aluminum oxide, silicon carbide, congruent melting.Abrasive particle also can comprise as at United States Patent (USP) 4,652, the abrasive material granule that discloses in 275 and 4,799,939.

First binding agent is formed by first binder precursor.Term " precursor " is meant uncured and uncrosslinked binding agent.Term " crosslinked " is meant to have the material that is cross-linked to form the polymer moieties of three-dimensional molecular network by chemical bond (being the interchain key).Be in its uncured state when therefore, first binder precursor is applied on the backing.First binding agent generally comprises curing or crosslinked thermosetting polymer.For the application, " curing " and " polymerization " commutative use.Yet at suitable treatment condition and catalyzer, first binder precursor can be cross-linked to form thermosetting adhesive.For the present invention, first binder precursor is " but energy solidified ", " curable " or " uncured ", and this is meant that this precursor can carry out crosslinked (promptly solidifying) under radiation (as actinic radiation, electron beam irradiation and/or thermal radiation) irradiation.

In addition, under suitable treatment condition, first binder precursor is a hot melt pressure sensitive adhesive.For example, look the chemical property difference, first binder precursor at room temperature can be a solid.For example, first binder precursor solid film that can be transfer coating to the backing.When being heated to high temperature, this first binder precursor can flow, and increases the viscosity of hot melt pressure sensitive adhesive.If perhaps for example resin contains solvent, first binder precursor at room temperature can be a liquid.

In an embodiment of the invention, first binder precursor that is used for the initial adhesive coating prescription of coated abrasive article of the present invention better is included in the hot melt pressure sensitive adhesive composition that can solidify the initial adhesive coating of thermoset that produces covalent cross-linking under the energy exposure.Since under suitable operational condition first binder precursor can hot-melt composition coating, first binder precursor is difficult for infiltrating through in the backing, with the intrinsic flexibility of induced damage resistive backing and flexible.Therefore, when being used in combination with porous cloth, fabric or textiles backing, the binder precursor that is disclosed among the present invention is particularly useful.Yet first binder precursor is penetrated into the good adhesive property that will help in the backing improving with backing to a certain extent.This penetration degree depends in part on particular chemical character and processing conditions, and can be controlled.

The term " porous " relevant with backing used among the application is meant there is not abrasive material, initial adhesive coating, bonding coat, sealing ply, saturated coating, the backing of pre-sizing menting property and gum knot coating etc. is using the Gurley Permeometer (available from Teledyne Gurley, Inc., Troy, New York) by federal No. 191 standard test methods, has Gurley porosity during method 5452 (publication on December 31 nineteen sixty-eight) (seeing also the Wellington Sears Handbook of Industrial Textiles that E.R.Kaswell write in 1963, the 575th page) test less than 50 seconds.For protecting cloth fiber and sealing backing, the cloth backing of present known coated abrasive article needs particular processing usually, as saturated coating, pre-sizing menting property, gum knot coating or primer knot coating.This backing also can not carry out these processing.Perhaps, this backing can carry out one or more above-mentioned processing.The type that backing and backing are handled depends in part on the required performance of intended purpose.The initial adhesive coating of hot melt of the present invention can provide these processing.

The pressure sensitive adhesion performance of the uncured initial adhesive coating of hot melt is adhered on the uncured initial adhesive coating abrasive particle before solidification process.The initial adhesive coating of thermoset after crosslinked is tough and tensile, but still deflection.And its dry adhesive is on backing.

Can be used for binder precursor among the present invention includes and is beneficial to the Resins, epoxy that improves the toughness of solidifying initial adhesive coating and weather resistance, can allows uncured initial adhesive coating show pressure-sensitive-adhesive and the thermoplastic resin of better being made up of vinyl-vinyl acetate copolymer (EVA) basically and is used for the fill a prescription catalyzer of epoxy moieties of initial adhesive coating.Randomly, binder precursor of the present invention also can comprise the pressure-sensitive-adhesive that is used to provide extra and with the thermoplastic polyester of EVA and epoxy resin compatibility, be used to improve the curing speed of initial adhesive coating and/or inflexible hydroxyl material, tackifier, filler etc.

The preferred binder precursor of the present invention contains have an appointment 45-95% weight ring epoxy resins and about 5-55% weight vinyl-vinyl acetate copolymer, and weight percentage is a benchmark by total resin content.Preferred binder precursor contains have an appointment 70-95% weight ring epoxy resins and about 5-30% weight vinyl-vinyl acetate copolymer, and does not contain material containing hydroxy groups, and weight percentage is a benchmark by total resin content.

Other preferred binder precursor contains the 50-94% weight ring epoxy resins of having an appointment, about 5-50% weight vinyl-vinyl acetate copolymer and about 0.1-15% weight polyfunctional acrylic ester component among the present invention, and weight percentage is a benchmark by total resin content.Other preferred binder precursor contains the 70-92% weight ring epoxy resins of having an appointment, about 5-30% weight vinyl-vinyl acetate copolymer and about 3-15% weight polyfunctional acrylic ester component among the present invention, and weight percentage is a benchmark by total resin content." total resin content " is meant the summation of Resins, epoxy, EVA multipolymer and many acrylate component (if present).

Resins, epoxy

The Resins, epoxy that can be used for binder composition of the present invention is to comprise at least one can pass through ring-opening reaction polymeric oxyethane ring, promptly

Any organic compound.These compounds broadly are called epoxide, not only comprise monomeric epoxide but also comprise the polymeric epoxide, can be aliphatic epoxide, alicyclic ring class (alicyclic) epoxide, heterocyclic epoxide, aromatic epoxide, also can be their mixture.They can be liquid or solid or their mixture, and this mixture can be used for preparing the tacky adhesion film.These each molecules of material average have at least two epoxy group(ing), so be also referred to as " polyepoxide ".These epoxide polymerizations comprise simple linear polymer (as the diglycidylether of polyoxyalkylenes glycol) with terminal epoxy groups group, have the polymkeric substance (as the polyhutadiene polyepoxide) of skeletal oxirane unit and have the polymkeric substance (as glycidyl methacrylate polymkeric substance or multipolymer) of epoxy side group.The molecular weight of Resins, epoxy can be about 74-100, and 000 or higher.The mixture of various Resins, epoxy also can be used in the hot-melt composition of the present invention." on average " number of epoxy group(ing) is defined as the sum of the number of epoxide group in the Resins, epoxy divided by the epoxy molecule in each molecule.

Useful Resins, epoxy comprises the Resins, epoxy that contains the cyclohexene oxide group, as epoxycyclohexane carboxylate, be typically 3,4-epoxy cyclohexane carboxylic acid 3,4-epoxycyclohexyl methyl esters, 3,4-epoxy-2-methylcyclohexanecarboxylic acid 3,4-epoxy-2-methylcyclohexyl methyl esters, hexanodioic acid two (3,4-epoxy-6-methylcyclohexyl first) ester.The more detailed situation of relevant this useful epoxide can be referring to United States Patent (USP) 3,117,099.

Useful especially other Resins, epoxy comprises the Racemic glycidol ether monomer of representing with following general formula in the invention process: R ' is (as aryl) or their combination of aliphatic (as alkyl), aromatics in the formula, and n is the integer of 1-6.Example is the polyphenol glycidyl ether that polyphenol and excess chlorine ethanol (as Epicholorohydrin) reaction make, as 2, and the diglycidylether of 2-two (4-hydroxy phenyl) propane (dihydroxyphenyl propane).Other case description that can be used for this class epoxide in the invention process is in United States Patent (USP) 3,018, in 262.Preferred Resins, epoxy comprises the diglycidylether of dihydroxyphenyl propane.

There are many commercially available Resins, epoxy to can be used among the present invention.Specifically, the epoxide that is easy to obtain comprises octadecylene oxygen, Epicholorohydrin, Styrene oxide 98min., the oxyethylene group tetrahydrobenzene, glycidyl methacrylate, bisphenol A diglycidyl ether is (as with trade(brand)name " EPON 828 ", " EPON 1004 " and " EPON 1001F " are available from Shell Chemical Co., Houston, the product of TX and with " DER-332 " and " DER-334 " available from Dow Chemical Co., Midland, the product of MI), the Bisphenol F diglycidylether (as with trade(brand)name " ARALDITE GY281 " available from Ciba-Geigy Corp., Hawthorne, NY and with " EPON 862 " product available from Shell Chemical Co.), vinyl cyclohexene dioxide (as with trade(brand)name " ERL 4206 " available from Union Carbide Corp., Danbury, the product of CT), 3,4-epoxy cyclohexene carboxylate 3,4-epoxycyclohexyl methyl esters (as with the product of trade(brand)name " ERL-4221 ") available from Union CarbideCorp., 2-(3,4-epoxycyclohexyl-5,5-spiral shell-3, the 4-epoxy) hexanaphthene-1,3-diox (with the product of trade(brand)name " ERL-4234 ") available from Union Carbide Corp., hexanodioic acid two (3,4-epoxy hexamethylene) ester (as with trade(brand)name " ERL-4299 " available from Union Carbide Corp), titanium dioxide kautschin (with the product of trade(brand)name " ERL-4269 ") available from Union Carbide Corp., epoxidized polybutadiene (with the product of trade(brand)name " OXIRON 2001 ") available from FMC Corp., epoxy silane, as β-3,4-epoxycyclohexyl ethyl trimethoxy silane and γ-glycidoxypropyltrime,hoxysilane (available from UnionCarbide), flame retardant epoxy resin (as the brominated bisphenol type Resins, epoxy of commodity " DER-542 " by name) available from Dow Chemical Co., 1,4-butanediol diglycidyl ether (as with the product of trade(brand)name " ARALDITERD-2 ") available from Ciba-Geigy Corp, the polyglycidyl ether of A Hydrogenated Bisphenol A-Epicholorohydrin basic ring epoxy resins (as with the product of trade(brand)name " EPONEX 1510 ") and lacquer resins (as with trade(brand)name " DEN-431 " and " DEN-438 " product) available from Dow Chemical Co. available from Shell Chemical Co..

The thermoplastic component of binder precursor of the present invention and initial adhesive coating resin comprises, but better is made of one or more thermoplastic ethylene-vinyl acetate copolymer resins basically.Ethane-acetic acid ethyenyl ester (" EVA ") multipolymer is well-known, and can make by the high-pressure free radical copolyreaction with vinyl-acetic ester as known in the art and ethene.Useful EVA multipolymer comprises that vinyl acetate unit content is no less than about 30% weight, generally is no less than about 40% weight, better is no less than 50% weight, better is no less than the multipolymer of 60% weight.Useful EVA multipolymer comprises that also vinyl acetate content is a 20-99% weight, is preferably 40-95% weight, and 50-90% weight more preferably is preferably the multipolymer of 60-80% weight.

The EVA multipolymer has many commercial source, as with trade(brand)name " ELVAX " available from E.I.Du Pont deNemours and Co. (Wilmington, DE), with trade(brand)name " LEVAPREN " available from Bayer Corp. (Pittsburgh, PA) and available from AT Plastics, Inc. (Ontario, Canada).

The limiting examples that can be used for the commercially available EVA multipolymer in the invention process comprises AT Plastics3325M EVA multipolymer (33% weight vinyl-acetic ester); ELVAX ^TM40W and LEVAPREN ^TM400 (40% weight vinyl-acetic esters); LEVAPRENTM 450,452 and 456 (45% weight vinyl-acetic ester); LEVAPREN ^TM500HV (50% weight vinyl-acetic ester); LEVAPREN ^TM600 HV (60% vinyl-acetic ester); And LEVAPREN ^TM700HV (70% weight vinyl-acetic ester).

The component that is used to prepare binder precursor composition of the present invention that contains Resins, epoxy and EVA is compatible under molten state." compatible " is meant that the molten mixture of at least a Resins, epoxy and thermoplastic component is monophasic, and what promptly do not have to aware between each component is separated, and forms the uniform mixture of molten component.Certainly, the those of skill in the art in this area need not the content that too many experiment just can easily change vinyl-acetic ester in Resins, epoxy, EVA multipolymer and catalyst concentration and the multipolymer that is used to form homogeneous composition of the present invention.For example, the single-phase composite when keeping molten state, those of skill in the art generally can increase the concentration of vinyl-acetic ester in the EVA multipolymer with the increase of Resins, epoxy concentration in the uncured composition in this area.

In order to adapt to specific purposes, also can change the specific physicals of the cured binders that contains Resins, epoxy and EVA multipolymer by the ratio of regulating above-mentioned each component.In general, increase the relative content of EVA multipolymer in prescription, can increase viscosity (tack) and, and reduce the liquidity preference in the solidification process the binding property on high-energy surface.Liquid epoxies also can influence said composition viscosity to the plasticising amount of EVA multipolymer.The selective light catalyst consumption is to optimize the homogeneity in curing speed and the solidification process.Therefore, look required in the final composition performance, the relative quantity of mentioned component is carried out balance.

" polyfunctional acrylic ester " component in embodiment of binder precursor composition of the present invention is meant ester cpds, and it is aliphatic series polyol and (methyl) acrylic acid reaction product.Aliphatic series polyol comprises the compound of (gathering) aklylene glycol and (gathering) glycerine and so on.

(methyl) vinylformic acid is undersaturated carboxylic acid, and it for example comprises the carboxylic acid of representing with following basic form:

R is hydrogen atom or methyl in the formula.

Polyfunctional acrylic ester can be monomer or oligopolymer.For the present invention, term " monomer " thereby be meant has with identical or other monomer and forms little (lower molecular weight) molecule that chemical bond forms the capability of long-chain (polymeric chain or macromole).For the application, term " oligopolymer " thereby be meant has and forms chemical bond with identical or other oligopolymer and form the more polymer molecule that contains 2-10 repeating unit of the capability of long polymeric chain (as dipolymer, trimer, tetramer etc.).The mixture of monomer and oligopolymer also can be used as the polyfunctional acrylic ester component.The polyfunctional acrylic ester component better is a monomer component.

Representational polyfunctional acrylic ester monomer illustrative and comprising without limitation: glycol diacrylate, ethylene glycol dimethacrylate, hexanediyl ester, triethylene glycol diacrylate, Viscoat 295, ethoxylated trimethylolpropane triacrylate, glycerol tri-acrylate, pentaerythritol triacrylate, pentaerythritol acrylate trimethyl, tetramethylol methane tetraacrylate, tetramethylolmethane tetramethyl-acrylate and neopentylglycol diacrylate.The mixture of dissimilar polyfunctional acrylic esters and composition also can use.Term " acrylate " used among the application comprises acrylate and methacrylic ester.

Useful commercially available polyfunctional acrylic ester comprises the Viscoat 295 of commodity " SR351 " by name, the ethoxylated trimethylolpropane triacrylate of commodity " SR454 " by name, the tetramethylol methane tetraacrylate of commodity " SR295 " by name and the neopentylglycol diacrylate of commodity " SR247 " by name.Above-mentioned product is all available from Sartomer Co., Exton, PA.

Because have a plurality of functionality available on each monomer, the polyfunctional acrylic ester monomer can be solidified into reticulated structure rapidly.If an acrylate functionalities is only arranged, produce the non-netted molecule of line style during curing.In the present invention in order to promote the formation of required polymer network, the polyfunctional acrylic ester that preferably has two or more functionality.

Useful multifunctional acrylate oligomers comprises commercially available polyether oligomers, as the Macrogol 200 diacrylate of commodity " SR259 " by name and the poly(oxyethylene glycol) 400 diacrylate of commodity " SR344 " by name, both are all available from Sartomer Co., Exton, PA.

Other oligopolymer comprises acrylated Resins, epoxy, as the Resins, epoxy diacrylate, as the diacrylate of bisphenol A epoxide resin.The example of commercially available acrylated Resins, epoxy comprises with trade(brand)name " EBECRYL3500 ", " EBECRYL 3600 " and " EBECRYL 3700 " available from UCB Chemicals Corp., Smyrna, the Resins, epoxy of GA.

In general, the optimum amount of polyfunctional acrylic ester in the binder precursor composition is directly proportional with the acrylate equivalent, is inversely proportional to acrylate functionalities.

Behind the uv-radiation, has higher viscosity based on Resins, epoxy and vinyl-vinyl acetate copolymer and the binder precursor composition that contains polyfunctional acrylic ester.This specific character can be finely tuned the relative rate of curable epoxide and resin flows, thereby can control abrasive particle degree of wetting and orientation.As general preparation policy, the polyfunctional acrylic ester of use very little, binder precursor may flow too fast, can wetting well abrasive particle, thereby abrasive particle is embedded under the coating, for thicker coating especially like this.

Use too many polyfunctional acrylic ester, binder precursor can not fully flow with wetting abrasive particle before the epoxy component completely solidified.In this case, even uncured binder precursor at room temperature is an aggressive tack, but because the rheological of irradiation back resin has hindered wetting and very poor to the binding property of abrasive particle.On the other hand, the consumption that increases Resins, epoxy with respect to ethane-acetic acid ethyenyl ester component and polyfunctional acrylic ester component may make the binding agent rigidity after the curing higher.Therefore, the relative consumption of these three kinds of components is looked final the required performance of binding agent and is carried out balance.

Catalyzer of the present invention better activates with photochemical method, as activating with actinic radiation (wavelength is in the ultraviolet of electromagnetic spectrum or the radiation of visible part).Useful photocatalyst is divided into two classes: salt or positively charged ion organic metal salt, both all are described in United States Patent (USP) 5,709, in 948.

The salt light trigger that is used for cationoid polymerisation comprises iodine and sulfonium complex salt.Useful aromatics iodine complex salt is represented with following general formula: In the formula

Ar ¹And Ar ²Can be identical or different, they are the aryl that contain 4-20 carbon atom, and are selected from phenyl, thienyl, furyl and pyrazolyl;

Z be selected from oxygen, sulphur, C-C, In the formula R can be aryl (containing 6-20 carbon atom) or acyl group (containing 2-20 carbon atom) as ethanoyl, benzoyl as phenyl and R in the formula ₁And R ₂Be selected from hydrogen, contain 1-4 carbon atom alkyl, contain the alkenyl of 2-4 carbon atom;

M is zero or 1;

The general formula of X is DQ _n, D is metal in the periodic table of elements (chemical abstracts version) the IB-VIII family or the metalloid in the IIIA-VA family in the formula, and Q is a halogen atom, and n is an integer among the 1-6.Described metal better is copper, zinc, titanium, vanadium, chromium, magnesium, manganese, iron, cobalt or nickel, and described metalloid better is boron, aluminium, antimony, tin, arsenic and phosphorus.Halogen Q better is chlorine or fluorine.The example of suitable anion is BF ₄ ^-, PF ₆ ^-, SbF ₆ ^-, FeCl ₄ ^-, SnCl ₅ ^-, AsF6 ^-, SbF ₅OH ^-, SbCl ₆ ^-, SbF ₅ ^-2, AlF ₅ ^-2, GaCl ₄ ^-, InF ₄ ^-, TiF ₆ ^-2, ZrF ₆ ^-, CF ₃SO ₃ ^-Deng.Negatively charged ion better is BF ₄ ^-, PF ₆ ^-, SbF ₆ ^-, AsF ₆ ^-, SbF ₅OH ^-And SbCl ₆ ^-Negatively charged ion is more preferably SbF ₆ ^-, AsF ₆ ^-And SbF ₅OH ^-

Ar ¹And Ar ²Aryl can randomly contain one or more benzo rings (as naphthyl, benzothienyl, dibenzothiophene base, benzofuryl, dibenzofuran group etc.) that condense.If necessary, aryl also can be replaced by one or more non-basic groups, if these groups do not react with epoxide and hydroxy functional group basically.

Useful aromatics iodine complex salt is documented in United States Patent (USP) 4,256 in more detail, in 828.Preferred aromatics iodine complex salt is (Ar) ₂IPF ₆(Ar) ₂ISbF ₆

Aromatics iodine complex salt useful among the present invention is a photosensitive in the UV spectrum zone only.Yet, but they can be used to the sensitizing agent sensitization of known photodissociation Organohalogen compounds to spectrographic near ultraviolet and visible-range.Illustrative sensitizing agent comprises United States Patent (USP) 4,250, aromatic amine described in 053 and colored aromatics polynuclear hydrocarbon.

Be applicable to that aromatic sulfonium complex salt initiator of the present invention can represent with following general formula:

In the formula

R ₃, R ₄And R ₅Can be identical or different, as long as at least one group is an aryl.The aryl of the optional self-contained 4-20 carbon atom of these groups (as replacing and unsubstituted phenyl, thienyl and furyl) and contain the alkyl of 1-20 carbon atom." alkyl " speech comprises the alkyl (as the substituting group of halogen, hydroxyl, alkoxyl group and aryl and so on) of replacement.R ₃, R ₄And R ₅It better all is aryl;

Z, m and X define according to above-mentioned iodine complex salt.

If R ₃, R ₄And R ₅Be aryl, it can randomly have one or more benzo rings (as naphthyl, benzothienyl, dibenzothiophene base, benzofuryl, dibenzofuran group etc.) that condense.If necessary, aryl also can be replaced by one or more non-basic groups, if these groups do not react with epoxide and hydroxy functional group basically.

Salt that triaryl replaces such as hexafluoro-antimonic acid triphenylsulfonium and hexafluoro-antimonic acid are preferred sulfonium salts to phenyl thiophenyl phenylbenzene sulfonium.Useful sulfonium salt is described in greater detail in United States Patent (USP) 5,256, in 828.

Aryl sulfonium complex salt used among the present invention is a photosensitive in the UV spectrum zone only.Yet they can be by United States Patent (USP) 4,256,828 and 4,250, and the sensitizing agent sensitization described in 053 is to spectrographic near ultraviolet and visible-range.

Be applicable to that photoactivation organo-metallic complex salt of the present invention comprises United States Patent (USP) 5,059,701,5,191,101 and 5,252, the complex salt described in 694.These organo-metallic cationic salts have following general formula:

[(L ¹) (L ²) M ^m] ^{+ e}X ^-M in the formula ^mExpression is selected from the atoms metal of periodic table of elements IVB, VB, VIB, VIIB and VIII family element, better is Cr, Mo, W, Mn, Re, Fe and Co;

L ¹Expression does not have, one or two provides the part of π-electronics, and these parts can be identical or different, and is selected from and replaces and unsubstituted acyclic and cyclic unsaturated compound and group and replacement and unsubstituted carbocyclic aromatic and heterocyclic aromatic compounds.Every kind of compound can both provide 2-12 π-electronics to the valence shell of atoms metal M.L ¹Better be selected from and replace and unsubstituted η ³-allyl group, η ⁵-cyclopentadienyl, η ⁷-cycloheptatriene based compound and η ⁶Aromatic substance; Described η ⁶Be selected from η ⁶The η of-benzene, replacement ⁶-benzene compound (as dimethylbenzene) and compound with 2-4 fused rings; Each compound can both be to M ^mValence shell 3-8 π-electronics is provided;

L ²The part that expression does not have or 1-3 can provide even number π-electronics; These parts can be identical or different, and be selected from the derivative of carbon monoxide, nitrous, triphenyl phosphine, triphen  and phosphorus, arsenic and antimony, and condition is by L ¹And L ²To M ^mThe total elementary charge that provides makes title complex produce e net surplus positive charge; With

E is 1 or 2 integer, the residual electric charge of complex cation;

X is aforesaid halogen-containing complex anion;

The example that is suitable for the organometallic ligand cationic salts of making photoactivation catalyzer among the present invention comprises:

(η ⁶-benzene) (η ⁵-cyclopentadienyl) Fe ^{+ 1}SbF ₆ ^-

(η ⁶-toluene) (η ⁵-cyclopentadienyl) Fe ^{+ 1}AsF ₆ ^-

(η ⁶-dimethylbenzene) (η ⁵-cyclopentadienyl) Fe ^{+ 1}SbF ₆ ^-

(η ⁶-cumene) (η ⁵-cyclopentadienyl) Fe ^{+ 1}PF ₆ ^-

(η ⁶-dimethylbenzene (mixed isomers)) (η ⁵-cyclopentadienyl) Fe ^{+ 1}SbF ₆ ^-

(η ⁶-dimethylbenzene (mixed isomers)) (η ⁵-cyclopentadienyl) Fe ^{+ 1}PF ₆ ^-

(η ⁶-o-Xylol) (η ⁵-cyclopentadienyl) Fe ^{+ 1}CF ₃SO ₃ ^-

(η ⁶-m-xylene) (η ⁵-cyclopentadienyl) Fe ^{+ 1}BF ₄ ^-

(η ⁶-) (η ⁵-cyclopentadienyl) Fe ^{+ 1}SbF ₆ ^-

(η ⁶-hexamethyl-benzene) (η ⁵-cyclopentadienyl) Fe ^{+ 1}SbF ₅OH ^-With

(η ⁶-fluorenes) (η ⁵-cyclopentadienyl) Fe ^{+ 1}SbF ₆ ^-

Be applicable to that the preferred organo-metallic complex cation salt among the present invention comprises following one or more salt: (η ⁶-dimethylbenzene (mixed isomers)) (η ⁵-cyclopentadienyl) Fe ^{+ 1}SbF ₆ ^-, (η ⁶-dimethylbenzene (mixed isomers)) (η ⁵-cyclopentadienyl) Fe ^{+ 1}PF ₆ ^-, (η ⁶-dimethylbenzene) (η ⁵-cyclopentadienyl) Fe ^{+ 1}SbF ₆ ^-(η ⁶-) (η ⁵-cyclopentadienyl) Fe ^{+ 1}SbF ₆ ^-

Useful commercially available initiator comprises FX-512 ^TM(3M company, St.Paul, MN), CD-1010 ^TMAnd CD-1012 ^TM(Sartomer, Exton, PA) aromatic sulfonium complex salt, UVI ^TM-6974, and the aromatic sulfonium complex salt (Union Carbide Corp., Danbury, CT) and IRGACURE ^TM261, and positively charged ion organo-metallic complex salt (Ciba Geigy Chemicals, Hawthorne, NY).

If use, the consumption of light trigger is about 0.01-10% weight among the present invention, better is about 0.01-5% weight, preferably is about 0.5-2% weight, is benchmark with the gross weight of all resins of composition.

When the catalysis light trigger that is used for cured epoxy resin was the metallocene salt catalyzer, though choose wantonly, better and promotor (as United States Patent (USP) 5,436, the tertiary alcohol barkite described in 063) was used together.Available barkite promotor comprises United States Patent (USP) 5,252, the promotor described in 694.By the gross weight of Resins, epoxy and vinyl-vinyl acetate copolymer, this promotor better accounts for the 0.1-4% weight of adhesive composition.

Though the preferred consolidation agent of Resins, epoxy is the cationic photopolymerization catalyzer, the heat-activated curing agent of some Resins, epoxy (epoxide is solidified and crosslinked compound) can be used among the present invention.Under the temperature of these solidifying agent when component is mixed more fortunately is heat-staple.

Suitable thermal curing agents comprises aliphatic series and primary aromatic amine and secondary amine, as two (4-amino-benzene) sulfone, two (4-amino-benzene) ether and 2, and two (4-aminophenyl) propane of 2-; Aliphatic series or aromatic uncle amine are as dimethylaminopropylamine; Fluorenediamine, as United States Patent (USP) 4,684, the fluorenediamine described in 678; Boron trifluoride complex is as BF ₃Et ₂O and BF ₃H ₂NC ₂H ₄OH; Imidazoles, as Methylimidazole, hydrazine is as oneself two hydrazines; And guanidine, as tetramethyl guanidine and Dyhard RU 100 (dicyanodiamide are also referred to as DiCy usually) and their mixture.

Useful commercially available thermal curing agents comprises AMICURE ^TMCG-1200, Dyhard RU 100 (Air Products andChemical, Allentown, PA) and CUREZOL ^TM2MZ-AZINE, 2,4-diamino-6 (2 '-methylimidazolyl-(1 ')) ethyl-s-triazine (Air Products and Chemicals).

Thermal curing agents of the present invention better contains the 1-25% weight of having an appointment, better contain the 2-20% weight of having an appointment, preferably contain one or more thermocatalysts of 3-15% weight of having an appointment, this weight percentage by Resins, epoxy, ethane-acetic acid ethyenyl ester component and polyfunctional acrylic ester component (if any words) gross weight be benchmark.

Under the situation of the polyfunctional acrylic ester component of free-radical curable, also can be used for causing and producing free radical though be to be understood that electron beam source, can in initial adhesive coating precursor, add radical initiator.By the total amount of resin Composition, the add-on of radical initiator is preferably 0.1-3.0% weight.

The example that can produce the using light initiator of radical source when with UV-irradiation includes, but are not limited to organo-peroxide, azo-compound, quinone, benzophenone, nitroso compound, carboxylic acid halides, hydrazone, sulfhydryl compound, pyrylium compound, three acyl group imidazoles, acylphosphine oxide, two imidazoles, chlorine alkyl triazine, benzoin ether, benzil ketals, thioxanthone, acetophenone derivs and composition thereof.

The case description of light trigger that produces radical source under visible radiation irradiation is in United States Patent (USP) 4,735, in 632.Can use the preferred initiator that produces free radical with UV-light is with the initiator of trade(brand)name " IRGACURE 651 " available from Ciba Specialty Chemicals.

The example that produces the useful thermal initiator of radical source under the heat energy effect comprises azo, superoxide, persulphate and redox initiator.

Suitable azo initiator includes, but are not limited to 2,2 ＇-azo two (4-methoxyl group-2,4-methyl pentane nitrile) (VAZO33); 2,2 ＇-azo two (2-amidine propane) dihydrochlorides (VAZO 50); 2,2 ＇-azo two (2, the 4-methyl pentane nitrile) (VAZO52); 2,2 ＇-azo two (isopropyl cyanide) (VAZO 64); 2,2 ＇-azo two (2-methylbutyronitrile) (VAZO 67); 1,1 ＇-azo two (1-cyclohexane nitrile) (VAZO 88) (above-claimed cpd is all available from DuPontChemicals) and 2,2 ＇-azo two (methyl isobutyrate) is (available from Wako Chemicals) (V-601).

Suitable peroxide initiator comprises, but be not limited to Benzoyl Peroxide, acetylperoxide, peroxide lauroyl, peroxide caprinoyl, cross two carbonic acid, two cetyl, cross two carbonic acid two (4-tertiary butyl hexamethylene) ester (PERKADOX16S, available from Akzo Chemicals Inc.), cross two carbonic acid two (2-ethyl oneself) ester, (Lupersol 11 to cross the PIVALIC ACID CRUDE (25) tert-butyl ester, available from Atochem), the peroxide-2 ethyl hexanoic acid tert-butyl ester (Trigonox 21-C50, available from Akzo Chemicals, Inc.) and dicumyl peroxide.

Suitable persulfate initiator includes, but are not limited to Potassium Persulphate, Sodium Persulfate and ammonium persulphate.

Suitable redox initiator includes, but are not limited to the combination of above-mentioned persulfate initiator and reductive agent (as sodium metabisulfite and sodium bisulfite); System (Benzoyl Peroxide and xylidine) based on organo-peroxide and tertiary amine; And based on the system (as cumene hydroperoxide and cobalt naphthenate) of organic hydroperoxide and transition metal.

Other initiator includes, but are not limited to quite which alcohol, as tetraphenyl 1,1,2, and 2-ethylene glycol.

Preferred thermal free radical initiator is selected from azo-compound and superoxide.Most preferably V-601, Lupersol 11 and Perkadox 16S and composition thereof.

The consumption of initiator is a catalytically effective amount, and this consumption generally is about the 0.01-5 weight part, better is about the 0.025-2 weight part, is benchmark with the total adhesive composition of 100 weight parts.If use the mixture of initiator, the total amount of initiator mixture should be and only uses single consumption of planting initiator.

Randomly, binder precursor of the present invention also can contain thermoplastic polyester.Useful polyester components comprises that hydroxyl and carboxylic acid are the material of end group, and it can be amorphous or hemicrystalline.Wherein more preferably hydroxyl is the material of end group." amorphous substance " is meant the material that shows second-order transition temperature but can not show crystalline melt point with differential scanning calorimeter (DSC) measurement.This second-order transition temperature better is lower than the decomposition temperature (following) of initiator, but is no more than 120 ℃." hemicrystalline material " is meant that demonstration can show crystalline melt point with DSC, but maximum fusing point should be about 150 ℃ polyester components.

The viscosity of polyester components is important (opposite with the resin combination that the liquid that can measure viscosity is arranged under the room temperature) for the hot-melt adhesive precursor composition is provided.Therefore, be used for the brookfield viscosity in the time of 121 ℃ (on the #DV-II brookfield's viscometer that uses the #27 rotor to be connected, measuring) of the polyester components of binder precursor composition of the present invention above 10,000 millipoises (1000Pa.s) with thermoelectric cell.Viscosity is relevant with the molecular weight of polyester components.The number-average molecular weight of preferred polyester component is about 7500-200, and 000, better be about 10,000-50,000, preferably be about 20,000-40,000.

The polyester components that is used for binder precursor composition of the present invention contains the reaction product of di-carboxylic acid (or its diester deriv) and dibasic alcohol.Di-carboxylic acid can be saturated aliphatic acids (comprising the annular material that 5-6 atom arranged in straight chain, side chain or the ring) that contains the 4-12 carbon atom and/or the aromatic acid that contains 8-15 carbon atom.The more specifically case description of suitable polyester component and polyester material is in United States Patent (USP) 5,436,063.

The component (not comprising following additive) that is used to form binder precursor composition of the present invention is compatible under molten state." compatible " is meant that the molten mixture of each component is monophasic, promptly do not have visible to be separated between each component, forms the homogeneous mixture of molten component.Certainly, those skilled in the art need not too many experiment and just can easily change the concentration of the Resins, epoxy that is used for binder precursor composition of the present invention, EVA multipolymer and vinyl acetate content wherein, optional thermoplastic polyester and catalyst concentration.For example, for keeping the single-phase composite under the molten state, those skilled in the art generally increase the concentration of vinyl-acetic ester in the EVA multipolymer with the increase of Resins, epoxy concentration in the composition.

In order to adapt to specific purposes, also can change specific physical properties by the ratio of regulating above-mentioned each component.In general, increase the relative content of EVA multipolymer in the composition, can increase viscosity (tack) and, and reduce the liquidity preference in the solidification process the binding property on high-energy surface.The relative content that increases polyester in the adhesive composition generally can reduce viscosity, increases flowability, and improves the consistency of epoxy component and EVA copolymer component.The consumption of selecting catalyst is to optimize curing speed, the life-span of uncured product and the homogeneity in the solidification process.Therefore, look final character required in the cured binders, the relative consumption of mentioned component is carried out balance.

Randomly, binder precursor of the present invention also can contain the material of hydroxyl.The material of hydroxyl can be liquid or solid-state organic substance, and its functionality is at least 1, better is at least 2.The organic substance of hydroxyl should not contain the group that other contains " active hydrogen ", as amino and sulfydryl.The organic substance of hydroxyl also should not contain heat or the unsettled group of photochemistry, thereby is being lower than 100 ℃ temperature or is decomposing under energy effect in solidification process or discharge volatile component.

This organic substance better contains two kinds or a plurality of uncle or secondary aliphatic hydroxide radical (being that hydroxyl directly is connected with non-aromatic carbon atom).This hydroxyl can be positioned at the end of polymkeric substance or multipolymer or side joint in this polymkeric substance or multipolymer.The number average equivalent of hydroxyl material better is about 31-2250, better is about 80-1000, preferably is about 80-350.Better polyalkylene glycol and trivalent alcohol are used as the hydroxyl material.Preferably cyclohexanedimethanol is used as the hydroxyl material.

Hydroxy functionality is that the illustrative example of 1 suitable organic substance comprises an alkyl oxide of alkanol, polyoxyalkylenes glycol and an alkyl oxide of aklylene glycol.

The illustrative example of useful monomers poly-hydroxy organic substance comprises aklylene glycol (for example 1,2-ethylene glycol, 1, ammediol, 1,4-butyleneglycol, 2-ethyl-1,6-hexylene glycol, 1,4 cyclohexane dimethanol, 1,18-dihydroxyl octadecane and 3-chloro-1, the 2-propylene glycol), polyhydroxyalkanes (as glycerine, trimethylolethane, tetramethylolmethane and sorbyl alcohol) and other polyol (as N, N-two (hydroxyethyl) benzamide, castor-oil plant wet goods).

The illustrative example of useful hydroxyl polymer-containing comprises that polytetrahydrofuran diol, the hydroxyl of polyoxyalkylene polylol (as polyoxyethylene and polyoxypropylene diols and triol, the equivalent of glycol is that the equivalent of 31-2250 or triol is 80-350), different molecular weight are the polylactone of end for terminal polyester and hydroxyl.

Useful commercially available hydroxyl material comprises United States Patent (USP) 5,436, the hydroxyl material of record in 063.

The consumption of hydroxyl organic substance in binder precursor of the present invention looked various factors (as the equivalent of the consistency of hydroxyl material and Resins, epoxy and polyester components, hydroxyl material and functionality, finally solidify the required character of initial adhesive coating) and can be changed within a large range.

Second-order transition temperature and flexibility that the hydroxyl material that should choose wantonly is specially adapted to regulate the initial adhesive coating of hot melt of the present invention.When the equivalent of hydroxyl material increased, though cohesive strength can must reduce, the flexibility of the initial adhesive coating of hot melt correspondingly increased.Similarly, reducing equivalent can cause losing flexibility and must increase cohesive strength.Therefore, for these two kinds of character of balance, should select the equivalent of hydroxyl material.

Following illustrating in greater detail, the solidification rate of binder precursor when the adding polyether glycol is specially adapted to regulate energy exposure in binder precursor of the present invention.The polyether glycol (being the polyoxyalkylene polylol) that can be used for regulating solidification rate comprises the polytetrahydrofuran diol and the polyoxyalkylated dihydroxyphenyl propane of polyoxyethylene glycol and triol and polyoxypropylene diols and triol (equivalent for glycol is about 31-2250, is about 80-350 for the equivalent of triol), different molecular weight.

The relative quantity of optional hydroxyl organic substance is determined according to the hydroxy number in the binder precursor composition and the ratio of epoxy group(ing) number.This ratio can be 0: 1-1: 1, more preferably 0.4: 1-0.8: 1.Relatively large hydroxyl material has increased the flexibility of binder precursor, but has correspondingly reduced cohesive strength.If the hydroxyl material is a polyether glycol, increases consumption and can further reduce solidification rate.

In order to improve viscosity, can in the binder precursor composition, add tackifier.This tackifier can be rosin ester, aromatic resin or their mixture or other any suitable tackifier.The illustrative example that can be used for rosin ester tackifier of the present invention comprises esterase, rosin pentaerythritol ester and their hydrogenated products.The illustrative example of aromatic resin tackifier comprises alpha-methyl styrene resin, styrene monomer, polystyrene, cumarone, indenes and Vinyl toluene.Preferred tackifier are hydrogenated wood rosin glycerol esters.

Useful tackifier resins type comprises by the rosin of pine tree acquisition and the organic acid of rosin derivative and abietic acid and Korean pine acid type, they can be esterified, hydrogenation or polymerization (molecular weight reaches 2000), and with trade(brand)name " FORALS " available from Hercules Chemical or with trade(brand)name " SYLVATAC " available from ArizonaChemical Co.; By the terpenes of turps and Orange Peel (as α ﹠amp; Beta-pinene or limonene (limonene)), their cationically polymerizables (molecular weight is 300-2000) or carry out modification (terpene phenolic resin) with the C-9 monomer, and with trade(brand)name " PICCOLYTE " available from Hercules Chemical or with trade(brand)name " ZONATAC " available from Arizona Chemical Co.; Some aliphatic hydrocarbon resins, as aliphatic resin based on C-5 monomer (as piperylene or dicyclopentadiene), can trade(brand)name " WINGTACK " available from Goodyear Chemicals; Based on the aromatic resin of C-9 monomer (as indenes or vinylbenzene), can trade(brand)name " REGALREZ " available from Hercules Chemical or with trade(brand)name " ESCOREZ 2000 " available from Exxon Chemical, it can be hydrogenated (molecular weight is 300-1200).

If tackifier are used for first binder precursor, its consumption is counted the 0.1-40 weight part by the gross weight of first adhesive precursor, is preferably the 0.5-20 weight part.

Sizing menting property 20 is coated on abrasive particle 16 and the initial adhesive coating 18.This sizing menting property can contain cementing agent or solidified resin glue.The example of appropriate resin tackiness agent comprises resol, has α, the Resins, epoxy of the aminoplastics of β-unsaturated side joint group, urethane, acrylated urethane, Resins, epoxy, acrylated Resins, epoxy, isocyanuric acid ester, acrylated isocyanuric acid ester, urea-formaldehyde resin, melamine-formaldehyde resin, bismaleimides and fluorenes modification and their mixture.The precursor of sizing menting property also can contain catalyzer and/or the solidifying agent that is useful on the initiation and/or quickens following solidification process.Sizing menting property is to select according to the required character of final coated abrasive article.

Additive and filler

Initial adhesive coating and sizing menting property binder precursor also can contain various optional additives, as filler, grinding aid, fiber, lubricant, wetting agent, tensio-active agent, pigment, defoamer, dyestuff, coupling agent; Softening agent, suspension agent, if they do not influence the pressure-sensitive-adhesive (before the completely solidified) of initial adhesive coating or under the irradiation energy effect ability to cure to initial adhesive coating or sizing menting property do not have a negative impact.In addition, the consumption that adds these additives and these additives should not have a negative impact to the rheological of binder precursor.For example, add the processing characteristics that too many filler can influence initial adhesive coating.

Filler of the present invention must not influence the abundant curing of the resin system that contains it.The example of the useful filler of the present invention comprises silicon-dioxide, as quartz, granulated glass sphere, glass envelope and glass fibre; Silicate is as talcum, clay, (polynite) feldspar, mica, Calucium Silicate powder, calcium metasilicate, sodium aluminium silicate, water glass; Metal sulfate is as calcium sulfate, barium sulfate, sodium sulfate, aluminium sodium sulfate, Tai-Ace S 150; Plaster stone; Vermiculite; Wood powder; Aluminum trihydrate; Carbon black; Aluminum oxide; Titanium dioxide; Sodium aluminum fluoride; Chiolite; Metal sulphite (as calcium sulfite).Preferred filler is feldspar and quartz.

If use grinding aid in implementing process of the present invention, suitable grinding aid comprises sodium aluminum fluoride; Chiolite; Sodium aluminum fluoride ammonium, potassium tetrafluoroborate etc.

Abrasive material 14 also can contain the 3rd binding agent or go up sizing menting property 22.A kind of useful last sizing menting property comprises grinding aid (as potassium tetrafluoroborate) and tackiness agent (as Resins, epoxy).This sizing menting property of going up is documented in the disclosed european patent application 486,308 in more detail.Sizing menting property 22 is in order to prevent or to reduce gathering of smear metal between abrasive particle (lost material on the workpiece) in the increase.This smear metal meeting of gathering obviously reduces the cutting ability of abrasive product.Be used to prevent that the material that smear metal is gathered from comprising the metal-salt (as Zinic stearas or calcium stearate) of lipid acid, the salt of phosphoric acid ester (as phosphoric acid Shan Yu ester potassium), phosphoric acid ester, urea-formaldehyde resins, mineral oil, crosslinked silane, crosslinking silicone, fluorochemicals and their mixture.

A kind of optional gum knot coating 24 can be provided, and as non-skid finish, it contains the resin glue that is dispersed with filler particles.Perhaps, this gum knot coating can be to be used for coated abrasive article is bonded to pressure sensitive adhesive on the support pads of backing 12.The example of suitable pressure sensitive adhesive comprise latex, crepe, rosin, acrylic ester polymer (as, butyl polyacrylate and polyacrylic ester), acrylate copolymer (as Isooctyl acrylate monomer/vinylformic acid), vinyl ether (as the polyvinyl n-butyl ether), alkyd adhesives, rubber adhesive (as natural rubber, synthetic rubber and chlorinated rubber) and their mixture.The case history of coatings of pressure sensitive adhesive is at United States Patent (USP) 5,520, in 957.

Gum knot coating also can contain electro-conductive material, as the Vanadium Pentoxide in FLAKES in the binding agent (as sulfonated polyester), carbon black or graphite.The case description of useful conduction gum knot coating is in United States Patent (USP) 5,108,463 and United States Patent (USP) 5,137,452 in.

For improve initial adhesive coating 18 and/or gum the knot coating 24 (if any) binding property, need improve the surface that these layers are coated with.For example, if polymeric film is as backing, the surface of better improving this film, i.e. " priming paint ".Suitable surface improving method comprises corona discharge, UV-irradiation, electron beam irradiation, flame discharge and cut.

Manufacture method

Describe demonstration methods how to make abrasive product of the present invention as the lower section, particularly form the method for abrasive surface.

First binder precursor can prepare as follows: in a suitable vessel these components are mixed being enough to make under the high temperature of each component liquefaction, make their thorough mixing under agitation, but thermal destruction can not take place before the complete melting mixing of these components.This temperature section depends on specific chemical property.For example, this temperature can be 30-150 ℃, is generally 50-130 ℃, is preferably 60-120 ℃.These components can add simultaneously or successively, though better first mixed ethylene-vinyl acetate copolymer and solid epoxy resin, add then liquid-state epoxy resin, polyfunctional acrylic ester component (if any) and any optional hydroxyl material.Add catalyzer (as light trigger, photocatalyst and/or thermocatalyst) then, add optional additive (comprising filler or grinding aid) again.

This binder precursor should be compatible in uncured fusion mutually.In other words, before causing curing, the obvious visible that better do not have between each component is separated.This binder precursor can be after melting mixing directly use maybe can be packaged in bucket, drum or other suitable containers, better lucifuge before use.Bao Zhuan binder precursor can be delivered in the hot melts coating system with bucket unloading machine etc. like this.Perhaps uncured binder precursor of the present invention is transported in conventional body hot melt coater of clavate, ball shape, fritter shape, bulk, pillow or base shape and the feeding machine system.Though not necessarily preferred, also can in binder precursor, add organic solvent.

First adhesive precursor of the present invention also can be made into uncured, DNAcarrier free viscosity pressure sensitive adhesion film rolling.In this case, binder precursor is extruded, curtain coating or coating form film.This film can be used for the first binder precursor transfer coating to the abrasive product backing.Should use the release liner kraft paper of siloxanes (as scribble) to roll this adhesive membrane, it is packaged in light tightization radiating bag or other container then.

First binder precursor of the present invention can be applied on the abrasive product backing with extrusion coated machine, intaglio printing coating machine, coating machine (as with being coated with die head, heating scraper-type coating machine, roll coater, curtain formula coating machine, contrary roll-coater) or transfer coater.When being coated with, more about 50-125 ℃, better under about 80-125 ℃ temperature, be coated with initial adhesive coating with above-mentioned any method.

Binder precursor of the present invention can be made into stand alone type, DNAcarrier free pressure sensitive adhesion film.This film is transferable to be applied on the backing.If necessary, also can be before transfer coating it be die-cut to predetermined shape.Select the transfer coating temperature and pressure, with spilling of the degraded that reduces backing to greatest extent and initial adhesive coating.Said temperature and pressure can for room temperature to about 120 ℃ and about 30-250psi (2.1-17.8 kg/cm ²).A kind of typical situation is in room temperature and 100psi (7.0 kg/cm ²) condition under carry out transfer coating.For the porous backing, the transfer coating method is a kind of particularly preferred coating process.

Be coated with initial adhesive coating or binder precursor also belongs in the scope of the present invention with liquid, solution form, although this method is not preferred.The liquid-containing binder precursor can be applied on the backing with the technology (as rolling method, spraying method, mouthful pattern coating method, scraper type coating method etc.) of any routine.Behind the uncured initial adhesive coating that coating forms, the available energy shines it, to embed deactivated catalyst before the initial adhesive coating at abrasive particle.Perhaps, abrasive particle can be coated with after the initial adhesive coating binder precursor of coating and before partly solidified at once.

Initial adhesive coating of the present invention or the coating weight of binder precursor on backing are looked the grade of used abrasive particle and are different.For example, thinner abrasive particle generally needs less initial adhesive coating that abrasive particle is bonded on the backing.For bonding abrasive particle satisfactorily, must provide the binder precursor of capacity.Yet if the glue spread of binder precursor is too big, abrasive particle can partially or completely be immersed in the initial adhesive coating.This is undesirable.In general, the glue spread of binder precursor composition of the present invention (by solvent-free) is 4-300 gram/rice ², better be about 20-30 gram/rice ²

Initial adhesive coating binder precursor better is applied on the abrasive product backing with aforesaid method.And, in case with the material of energy irradiation coating, just cause at least Resins, epoxy and polyfunctional acrylic ester component (if any words) partly solidified.When shining binder precursor with the suitable energy, initial adhesive coating binder precursor begins to solidify, and then carries out for some time.Select the energy according to required processing conditions, and suitably activate epoxidation catalyst.This energy can be actinic energy (as the radiation of wavelength in ultraviolet or visible range), accelerated particle (as electron beam irradiation) or thermal source (heat or ir radiation).This energy better is actinic radiation (being the radiation of wavelength in ultraviolet or visible range).Suitable actinic radiation sources comprises mercury lamp, xenon lamp, carbon arc lamp, tengsten lamp, sunlight etc.

The uv-radiation of pressing mercuryarc lamp to send particularly is most preferred.Look the consumption of relevant reactant and kind, the energy, sheet stock speed, from the distance of the energy with need to solidify the thickness of initial adhesive coating and different, irradiation time be 1 second following to more than 10 minutes (better provide be about the 0.1-10 joule/centimetre ²(J/cm ²) total irradiation energy).

Binder precursor of the present invention also can be by being cured with the electron beam radiation irradiation.Required dosage is generally the 1-100 megarad.In the irradiation of the given energy or using the electron beam energy and do not using under the condition of light trigger, curing speed increases with the increase of photocatalyst and/or light trigger consumption.Curing speed also increases with the increase of energy intensity.

If the positively charged ion organic metal salt as the epoxy photocatalyst, is solidified even also can postpone under the situation that does not have polyvalent alcohol to exist.Can make binder precursor in the sufficiently long time, keep pressure-sensitive-adhesive like this, thereby after with energy irradiation binder precursor, still can allow above abrasive particle adheres to.

Abrasive particle can fully be cured in initial adhesive coating binder precursor and apply before no longer adhering to abrasive particle, though, generally shine initial adhesive coating binder precursor with the energy after, apply abrasive particle in a few times in second for the speed that improves industrial manufacturing processed need apply abrasive particle as early as possible.Abrasive particle can be according to the landing cladding process (drop coating) of routine techniques in this area, and more handy electrostatic coating method or magnetic cladding process apply.An example that can be used for making the method for abrasive product of the present invention can be referring to United States Patent (USP) 5,766,277.

By heating (as in baking oven) initial adhesive coating is carried out post curing treatment and can shorten the required time of completely solidified that reaches.After fixing also can influence the physicals of initial adhesive coating, generally is desirable therefore.The time of after fixing and temperature change with the factors such as second-order transition temperature, initiator concentration and energy exposure condition of vinyl-vinyl acetate copolymer.The longer time of several seconds to the lesser temps when condition of after fixing can be for 150 ℃ of left and right sides.Typical after fixing condition is following 1 minute of 100 ℃ of left and right sides temperature or shorter time.

In another kind of manufacture method, initial adhesive coating binder precursor is coated on the backing, then abrasive particle is embedded initial adhesive coating binder precursor, shine initial adhesive coating binder precursor with the energy again.

Available then various technology (as rolling method, spraying method, grooved roll coating method or curtain coating method) are coated on abrasive particle with sizing menting property 20 with flowable liquid form and above the initial adhesive coating, are cured by dry, heating or with electron beam or ultraviolet radiation irradiation then.Concrete curing is looked the chemical property of sizing menting property and is different.Can and solidify or dry optional last sizing menting property 22 by the similar methods coating.

Optional gum knot coating 24 can be coated on the backing 12 with various conventional coating techniques (being coated with method, scraper coating method, curtain coating method, woodburytype, hot substance transfer method, offset printing method, silk screen print method etc. as dip coating, rolling method, spraying method, Meyer rod).

In another kind of backing configuration, the back side of abrasive product can comprise a round base material.The purpose of this round base material provides a kind of means that make the firm interlock of hook on abrasive product and the support pads.Available any ordinary method is pressed in this round substrate layer on the abrasive material backing of coating.This round base material can carry out lamination before the initial adhesive coating precursor of coating or after the initial adhesive coating precursor of coating.

On the other hand, the round base material is the coated abrasive backing in essence.This round base material generally comprises the plane surface that has wreath, and these wreaths are from the rear side of plane surface lateral process forward.Initial adhesive coating precursor is coated on this plane surface.At this on the one hand, initial adhesive coating precursor directly is coated on the plane surface of round base material.In some cases, this round base material can comprise and is coated on the pre-sizing menting property that is used to seal this round base material on the plane surface.This pre-sizing menting property can be thermosetting polymer or thermoplastic polymer.Perhaps, this initial adhesive coating precursor can directly be coated on no wreath one side of non-tight round base material.This round base material can be made the round base material, extrude bonding round base material, make bonding round base material or napping round base material (as napping polyester or nylon) by snowy Neil.The example of conventional round backing is described in greater detail in United States Patent (USP) 4,609, in 581 and 5,254,194.

The round base material also comprises and is used for sealing the round base material on the plane surface and prevents that initial adhesive coating precursor infiltration from going into the seal coating of round base material.This round base material also comprises the thermoplasticity seal coating, and many vimentin filaments is arranged from thermoplasticity seal coating upper process.In fact these vimentin filaments form one deck fiber.These fibers better have from the arcuate section of fixed position spaced apart from each other with the equidirectional projection.In some cases, for fear of with conventional backing cost related problem, better directly be coated on the plane surface of round base material.Can prepare and be coated with initial adhesive coating binder precursor, so that initial adhesive coating precursor does not infiltrate through in the round base material significantly.Making like this has the initial adhesive coating precursor of capacity that abrasive particle is bonded on the round base material securely.

In like manner, the back side of abrasive product also can comprise many hooks.These hooks generally are the flat substrates with many hooks from the substrate backside projection.These hooks provide coated abrasive article and have comprised interlock means between the support pads of cast fabric.This hook-type base material can be laminated to the method for any routine on the coated abrasive backing.This hook-type base material can carry out lamination before or after applying initial adhesive coating.On the other hand, this hook-type base material is the coated abrasive backing in essence.In this case, initial adhesive coating precursor directly is coated on the hook-type base material.In some cases, for fear of with conventional backing cost related problem, better directly be coated on the hook-type base material.Relevant use hook-type backing or laminated other details of hook can be referring to United States Patent (USP)s 5,505, in 747.

Binder precursor of the present invention provides isostatic required character.As not solvent-laden preparation, the coating of the hot melts feeding device of their available routines.Therefore, they can be supplied as and be suitable for to being laminated to the pressure sensitive adhesion film on the backing.Comprise vinyl-vinyl acetate copolymer and provide pressure-sensitive-adhesive for binder precursor.Above this pressure-sensitive-adhesive helps abrasive particle is coated on.Add polyether glycol and give initial adhesive coating of the present invention, thereby after energy exposure, abrasive particle can be embedded binder precursor in the unlimited time (open time) of energy exposure with it with suitable molecular weight and functionality.In initial adhesive coating, add the controlling flow sex change well of polyfunctional acrylic ester component.

More particularly, used binder precursor preparation has lower cost, longer unlimited time and better film-forming properties than the initial adhesive coating that only contains Resins, epoxy and thermoplastic polyester among the present invention.As the result who improves film-forming properties, adhesive composition of the present invention needs less thermoplastic polyester in prescription, thereby has further reduced cost, and has improved the high-temperature behavior of this material.

Can understand the present invention more fully with reference to following non-restrictive example.In these embodiments, if do not explain in addition, all umbers, percentage ratio, ratio etc. are all by weight.

Used abbreviation has the implication shown in the following table among the embodiment.The DS1227 high molecular weight polyesters, commodity are called " DYNAPOL S1227 ", available from Creanova,

Piscataway, NJDS1402 high molecular and low-crystallinity polyester, commodity are called " DYNAPOL S1402 ", purchase

From Creanova, Piscataway, NJEL310 vinyl-vinyl acetate copolymer (25% vinyl-acetic ester), commodity are called " ELVAX

310 ", (commodity are called " ELVAX for Wilmington, DE) EL220 vinyl-vinyl acetate copolymer (28% vinyl-acetic ester) available from E.I.DuPont de Nemours and Co.

220 ", (commodity are called " ELVAX for Wilmington, DE) EL140 vinyl-vinyl acetate copolymer (33% vinyl-acetic ester) available from E.I.DuPont de Nemours and Co.

140 ", available from E.I.DuPont de Nemours and Co. (commodity are called " LEVAPREN 700 " for Wilmington, DE) L700 vinyl-vinyl acetate copolymer, available from

(commodity are called " EPON to Bayer Corp. for Pittsburgh, PA) E828 bisphenol A epoxide resin (epoxy equivalent (weight) is a 185-192 gram/equivalent)

828 ", available from Shell Chemical, Houston, TXE1001 bisphenol A epoxide resin (epoxy equivalent (weight) is a 525-550 gram/equivalent), commodity are called " EPON

1001F ", available from Shell Chemical, Houston, TXE4221 cycloaliphatic epoxy resin (epoxy equivalent (weight) is 126 gram/equivalents), commodity are called " ERL

4221 "; available from Union Carbide Corp.; Danbury, CTCHDM cyclohexanedimethanol TMPTA TriMethylolPropane(TMP), commodity are called " SR351 "; available from Sartomer Co.; Exton, PAKB1 2,2-dimethoxy-1; 2-phenylbenzene-1-ethyl ketone, with trade(brand)name " IRGACURE 651 "

Available from Ciba Specialty Chemicals or with trade(brand)name " KB1 " available from Sartomer

Co., Exton, PACOM hexafluoro-antimonic acid (1-) η ⁵-[dimethylbenzene (mixed isomers)] η ⁵-cyclopentadienyl closes iron

(1+) (as catalyzer) AMOX oxalic acid two tert-pentyl esters (as promotor) heat treated fused alumina of CRY sodium aluminum fluoride AO fused alumina HTAO

Testing sequence

Following embodiment and Comparative Examples are tested by following test method.

No. 1 test: Xi Fuer test method

It is 10.2 centimetres disk that the coated abrasive article of each embodiment is processed into diameter, and is fixed on the porous plastics support pads with pressure sensitive adhesive.Coated abrasive disk and support pads assembly are installed on the Xi Fuer trier, and with coated abrasive wafer grinding annular (donut) cellulose acetate butyrate polymkeric substance or 1018 soft steel workpiece.Load is 4.5 kilograms.The terminal point of test is 500 commentaries on classics or circle coated abrasive disk.The cellulose acetate butyrate amount of polymers that measurement grinds away when off-test.Testing the mineral collecting amount (mineral pick-up) and the cutting output that obtain among each embodiment that records with No. 1 lists in the following data.

Be used to form the melting mixing of EVA/ epoxy resin blend

Prepare 200 gram samples as follows: fusion EVA multipolymer in 100-150 ℃ and 1 quart of canister, add liquid-state epoxy resin then (if add E1001, earlier with its fusion), mix with the air mixed machine, add remaining liquid epoxies and cyclohexanedimethanol (CHDM is as the words that add) (in all embodiment that use CHDM, its consumption be total amount 2.4%), mix once more, temperature is reduced to 100-120 ℃, add CpFe dimethylbenzene then ⁺SF ₆ ^-(COM) and oxalic acid two tert-pentyl esters (AMOX).The consumption of the two kinds of compounds in back is respectively 0.6-1%.Serving as a contrast from (the silicone release layer on the PET film) on the lining resin-coated with hot scraper at 95-100 ℃, thickness is the 0.05-0.10 millimeter.Thicker sample is used for physicals test (DMA and DSC).Thin coating (0.05 millimeter) is laminated on the abrasive material backing, and this backing comprises 36 * 34 lines/centimetre utility cloth polycotton, shaft-like sheet stock base material and various paper backing.Except the initial adhesive coating resin that contains L700, all contain the initial adhesive coating resin of EVA multipolymer melting mixing.

Be used to form the solvent of EVA/ epoxy resin blend

By the 25-40% solids content L700 is dissolved in ethyl acetate or the butanone, adds Resins, epoxy and CHDM (as the words that add), fall solvent 60-90 ℃ of coupling vacuum stripping.At 100-120 ℃ the photocatalyst system is joined (add COM and AMOX, add-on respectively is 0.6-1%) in this melt, mix, be applied to then on the above-mentioned base material with the air mixed machine.Yet solvent resin glue of the present invention is not preferred, and the physical properties of solvent that records and melting mixing binding agent is expected in the experimental error scope.

The preferred blending means of the resin glue that vinyl-acetic ester EVA multipolymer content is higher is as follows: the EVA copolymer pellets is added rotate in the meshed double screw forcing machine fusion under 80-140 ℃ of temperature in the same way.Molten solids Resins, epoxy (E1001) sheet stock pumps into liquid form in the opening for feed in thermoplastic material downstream.At last, mix all other components (E828, COM, AMOX and optional CHDM, TMTPA and KB1) with batch mode at 75 ℃.The homogeneous liquid that forms is pumped in the forcing machine in solid epoxy and thermoplastic material downstream.Extrudate is collected in the case that is lined with siloxanes, is stored in the dark place with solid form under the room temperature.Can when further using, needs melt again easily like this.

Dynamic mechanical analysis (DMA)

Prepare sample by the curable hot melts of coating between the polyester release liner that is the 2-5 mil at two thickness.(Philips, B.V. is Holland) with about 3 joules/centimetre with TLD 15W/03 bulb by release liner ²Radiating capacity irradiation coating.The sample that will shine is placed in 100-110 ℃ the baking oven 30 minutes then, further to solidify.Film band after solidifying is cut into 1.0 centimetres of wide and about 2-3 cm long.Use be equipped with the tension specimen anchor clamps Seiko Instruments DMA 200 rheometers (Seiko Instruments, Torrance, CA).With separately 10 millimeters of chucks.Single-frequency and the rate of rise in temperature in-80 to 250 ℃ of scopes at 1Hz are 2 ℃/minute.The DMA data are listed among the table 1-3.

Table 1: the material character of melt-processable EVA/ Resins, epoxy

Prescription	% vinyl-acetic ester among the EVA	??????DMA ?????Tg(℃)	??DMA E′(25℃， ??MPa)	?DMA E′(100℃， ?MPa)
Prescription	% vinyl-acetic ester among the EVA	??????DMA ?????Tg(℃)	??DMA E′(25℃， ??MPa)	?DMA E′(100℃， ?MPa)	40%EVA (EL310) 60% Resins, epoxy	????25	???-30℃/134	??700	?300
40%EVA (EL220) 60% Resins, epoxy	????28	???-31℃/125	??130	?60	40%EVA (EL310) 60% Resins, epoxy	????25	???-30℃/134	??700	?300
40%EVA (EL220) 60% Resins, epoxy	????28	???-31℃/125	??130	?60	40%EVA (EL140) 60% Resins, epoxy	????33	???-28℃/116	??80	?20
10%EVA (L700) 90% Resins, epoxy (E828) does not contain CHDM	????70	???-3℃/150	??700	?300	40%EVA (EL140) 60% Resins, epoxy	????33	???-28℃/116	??80	?20
	????70	???-3℃/150	??700	?300	20%EVA (L700) 80% Resins, epoxy (E828) does not contain CHDM	????70	???53℃/125	??1000	?130
10%EVA (L700) 90% Resins, epoxy (E1001) does not contain CHDM	????70	?????110	??2100	?400		????70	???53℃/125	??1000	?130
	????70	?????110	??2100	?400	20%EVA (L700) 80% Resins, epoxy (E1001) does not contain CHDM	????70	?????117	??1300	?400

Table 2: the material character of the EVA/ epoxy blend of melt-processable

Prescription	% vinyl-acetic ester among the EVA	???DMA ??Tg(℃)	??DMA E′(25℃， ??MPa)	???DMA ?E′(100℃， ???MPa)
Prescription	% vinyl-acetic ester among the EVA	???DMA ??Tg(℃)	??DMA E′(25℃， ??MPa)	???DMA ?E′(100℃， ???MPa)	10%EVA (L700) 90% Resins, epoxy (E1001) CHDM	????70	????99	??1600	???30
15%EVA (L700) 85% Resins, epoxy (E1001) CHDM	????70	???101	??1400	???60	10%EVA (L700) 90% Resins, epoxy (E1001) CHDM	????70	????99	??1600	???30
15%EVA (L700) 85% Resins, epoxy (E1001) CHDM	????70	???101	??1400	???60	20%EVA (L700) 80% Resins, epoxy (E1001) CHDM	????70	????97	??1100	???20
25%EVA (L700) 75% Resins, epoxy (E1001) CHDM	????70	???102	??1100	???60	20%EVA (L700) 80% Resins, epoxy (E1001) CHDM	????70	????97	??1100	???20

The material character of table 3:EVA/ epoxy resin blend; The effect of sodium aluminum fluoride filler

Prescription	% vinyl-acetic ester among the EVA	???DMA ??Tg(℃)	??DMA E′(25℃， ??MPa)	???DMA ?E′(100℃， ???MPa)
Prescription	% vinyl-acetic ester among the EVA	???DMA ??Tg(℃)	??DMA E′(25℃， ??MPa)	???DMA ?E′(100℃， ???MPa)	15%EVA (L700) 85% epoxy (6: 4E1001: E828) do not contain CHDM	????70	???138	??1000	???600
12%EVA (L700) 68% epoxy (6: 4E1001: E828) do not contain CHDM 20% sodium aluminum fluoride	????70	???138	??1800	???860		????70	???138	??1000	???600
	????70	???138	??1800	???860	12%EVA (L700) 68% epoxy (6: 4E1001: E828) CHDM 20% sodium aluminum fluoride	????70	????97	??1400	???750
15%EVA (L700) 85% epoxy (6: 4E1001: E828) CHDM	????70	???123	??520	???290		????70	????97	??1400	???750

The physical properties of EVA/ epoxy blend shows that the most compatible blend is to contain the blend that vinyl acetate content is the EVA multipolymer about 70% weight.The preferred composition that is used for abrasive material is that to comprise EVA multipolymer, the EVA multipolymer that vinyl acetate content is about 60-80% weight be 10-20% weight and the composition that does not contain chainextender (CHDM) with respect to the concentration of Resins, epoxy.The Knoop hardness number of these materials (KHN) is about 10, can be comparable with the hardness value of epoxy/polyester/polyacrylic ester melt-processable resin system.Also can add filler; The purposes of sodium aluminum fluoride is listed in the table 3.Second-order transition temperature (Tg) after the preferred binder composition solidifies is very suitable for nonferromagnetic substance far above 60 ℃.

The preparation of comparative example A and embodiment 1

The comparative example A is available from Minnesota Mining and Manufacturing Company " 3M Grade P180 216 U Production Fre-CutA Weight paper ".Embodiment 1 comprises 115 gram/rice ²The paper backing is (available from Kammerer GmbH (Osnabruck, Germany)), P180 AO on initial adhesive coating of the initial adhesive coating of EVA/ epoxy resin blend (15%L700,85%E1001,0.6%COM and 0.6%AMOX), electrostatic applications, the sizing menting property (60%E828,20%E4221,20%DIPT and 1.0%COM) and the United States Patent (USP) 5 of radiation-hardenable, the abrasive construction that is called sizing menting property on the Zinic stearas of " A3469 " in 611,825.Representative (routine) coating wt is among the embodiment 1: initial adhesive coating weight=100 gram/rice ², mineral weight=120 gram/rice ², sizing menting property weight=50 gram/rice ², go up glued coating wt=25 gram/rice ²

The result is as follows for the Xi Fuer grinding test:

Embodiment Xi Fuer stock removal

(gram/500 changes)

The comparative example A 2.78

Embodiment 1 3.14

The grinding performance of embodiment 1 is comparative example A's grinding performance 13% roughly.

The preparation of Comparative Examples B and C and embodiment 2 and 3

At 140 ℃ Comparative Examples B and C are mixed.Just before coating, in this molten mixture, add acrylate, epoxidation catalyst and light trigger, mix.With embodiment 2 and 3 solvent (not being preferred); Resins, epoxy and EVA multipolymer are dissolved in the butanone.In vacuum drying oven, remove gradually and desolvate, temperature is risen to 120 ℃ simultaneously.After keeping 30 minutes under the condition of 120 ℃ of temperature and 1.0 torr vacuum tightnesss, suppose that all solvents are removed.Sample is transferred in the conventional baking oven, as the same other component that adds among Comparative Examples B and the C.Better as stated above with the sample melting mixing.Forming (weight part) lists in the table 4.

With scraper the coating of about 0.08 mm thick is applied to (150 gram/rice on the paper backing ², available from UPM-Kymmene, Pietarsaari, Finland).The temperature of scraper and coating bed all is about 130 ℃.With remaining embodiment 2 and 3 sample coating on the polyester release liner of siloxane treated, then at room temperature transfer coating on identical paper backing.The sample and the transfer coating that directly are coated on the backing are not having difference aspect mineral glue spread or the product performance between the sample on the backing.The initial adhesive coating weight of each sample is about 75 gram/rice ²

With the sheet stock speed irradiation coating of 236 watts of/centimetre Fusion Systems " D " bulb with 15 meters/minute.Electrostatic coating P80 HTAO level mineral (mineral) on the coating of shining then.At 120 ℃ initial adhesive coating was heated 10 minutes then, with the final curing resin.

The glued resin dispersion that will contain 40%E828,30%E4221,30%TMPTA, 1%KB1 and 1%COM is in butanone, then to be about 120 gram/rice ²The weight of (dry weight) is brushed on the sample.With the sample irradiation of 236 watts of/centimetre Fusion Systems " D " bulb after 15 minutes, solidified 10 minutes at 120 ℃ then these coatings.

Table 5 has been listed the P80 level mineral coating weight and the Xi Fuer experimental performance result of the foregoing description and Comparative Examples.

Table 4

Prescription	Comparative Examples B	Comparative Examples C	Embodiment 2	Embodiment 3
Prescription	Comparative Examples B	Comparative Examples C	Embodiment 2	Embodiment 3	DS 1227 (weight part)	????28	????21	????0	????0
L700 (weight part)	????0	????0	????28	????21	DS 1227 (weight part)	????28	????21	????0	????0
L700 (weight part)	????0	????0	????28	????21	E828 (weight part)	????37	????41	????39	????43
E1001 (weight part)	????26	????29	????27	????30	E828 (weight part)	????37	????41	????39	????43
E1001 (weight part)	????26	????29	????27	????30	CHDM (weight part)	????3	????3	????0	????0
TMTPA (weight part)	????3.8	????3.8	????3.8	????3.8	CHDM (weight part)	????3	????3	????0	????0
TMTPA (weight part)	????3.8	????3.8	????3.8	????3.8	KB1 (weight part)	????1	????1	????1	????1
COM (weight part)	????0.6	????0.6	????0.6	????0.6	KB1 (weight part)	????1	????1	????1	????1
COM (weight part)	????0.6	????0.6	????0.6	????0.6	AMOX (weight part)	????0.6	????0.6	????0.6	????0.6

Table 5

Sample	Mineral weight (gram/rice ²)	Soft steel Xi Fuer (stock removal: gram/500 changes)	CAB Xi Fuer (stock removal: gram/500 changes)
Sample	Mineral weight (gram/rice ²)	Soft steel Xi Fuer (stock removal: gram/500 changes)	CAB Xi Fuer (stock removal: gram/500 changes)	Comparative Examples B	????316	??????0.68	?????1.929
Comparative Examples C	????375	??????0.74	?????2.025	Comparative Examples B	????316	??????0.68	?????1.929
Comparative Examples C	????375	??????0.74	?????2.025	Embodiment 2	????418	??????0.66	?????1.617
Embodiment 3	????453	??????0.74	?????1.834	Embodiment 2	????418	??????0.66	?????1.617

Data show that the initial adhesive coating resin system in embodiment 2 and 3 is easier to bonding mineral grain than the initial adhesive coating resin system of Comparative Examples B and C in the table 5.Because the initial adhesive coating resin system of embodiment 2 and 3 has lower crystallization velocity than the initial adhesive coating resin system of Comparative Examples B and C, so they may have bigger viscosity in the longer time.

Known Xi Fuer test be acutance (mineral orientation) be again that anti-filling (anti-loading) is tested.Because the anti-filling additive (not existing among the present invention) around known, mineral orientation and dredge and be coated with (open coated) structure (being the structure that wear particle concentration is lower than 20-30%) and can improve anti-filling property can estimate to have the embodiment 2 of the higher mineral of concentration (being abrasive particle) coating and 3 grinding performance can not go with C than Comparative Examples B.

As if by comparing, the result of soft steel Xi Fuer test shows all four kinds of structure propertiess similar (enough), and be not subjected to the influence of mineral concentration and initial adhesive coating types of compositions.

Those skilled in the art are clear, can be used for various modifications and change the present invention under the condition that does not depart from the scope of the invention and essence.And, be to be understood that the present invention is not subjected to the inappropriate restriction of above-mentioned illustrated embodiment.

Claims

1. coated abrasive article comprises:

A) has the backing of front surface and rear surface;

2. the pre-glued backing that is used for the described coated abrasive article of claim 1 is characterized in that it comprises:

A) be applicable to the backing of coated abrasive article; With

3. coated abrasive article comprises:

A) has the backing of front surface and rear surface;

4. the pre-glued backing that is used for the described coated abrasive article of claim 3 is characterized in that it comprises:

A) be applicable to the backing of coated abrasive article; With

5. a method for preparing as claim 1 or 3 described coated abrasive articles is characterized in that it comprises the steps:

(a) provide backing with front surface and rear surface;

I) Resins, epoxy;

Ii) ethane-acetic acid ethyenyl ester; With

Iii) be used for crosslinked described curing agent for epoxy resin;

6. but composition as the energy solidified binder precursor of the described goods of claim 3 or the described pre-glued backing of claim 4 is characterized in that it makes by mixing following component:

A) Resins, epoxy;

B) ethylene-vinyl acetate copolymer resin;

C) polyfunctional acrylic ester component;

7. as claim 1 or 3 described coated abrasive articles, it is characterized in that it also is included in second binding agent on described first binding agent and the described abrasive particle.

8. as claim 1 or 3 described coated abrasive articles, as claim 2 or 4 described pre-glued backings, or the described composition of claim 6, it is characterized in that resin or melt composition that described first binder precursor is a melt-processable.

9. coated abrasive article as claimed in claim 1 is characterized in that described first binder precursor is the hot melt pressure sensitive adhesives.

10. as claim 1 or 3 described coated abrasive articles, as claim 2 or 4 described pre-glued backings, or the described composition of claim 6, it is characterized in that described solidifying agent is the acidic cationic photopolymerization catalyzer of energy, with the polymerization of the described Resins, epoxy of catalysis.

11. coated abrasive article as claimed in claim 1, pre-glued backing as claimed in claim 2 is characterized in that described vinyl-vinyl acetate copolymer contains and is no less than 30% weight vinyl-acetic ester.

12. coated abrasive article as claimed in claim 1, pre-glued backing as claimed in claim 2 is characterized in that described binder precursor also contains thermoplastic polyester.

13., it is characterized in that described coated abrasive article is the serial connection form that contains the many single mills that are interconnected to roller as claim 2 or 4 described coated abrasive articles.

14. coated abrasive article as claimed in claim 3, pre-glued backing as claimed in claim 4, or the described composition of claim 6 is characterized in that described first binder precursor also contains the reagent that is useful on crosslinked described polyfunctional acrylic ester.

15. coated abrasive article as claimed in claim 3, pre-glued backing as claimed in claim 4, or the described composition of claim 6 is characterized in that the described solidifying agent that is used for cross-linked epoxy resin is photocatalyst or thermal curing agents.

16. coated abrasive article as claimed in claim 15 is characterized in that described photocatalyst is the acidic cationic photopolymerization catalyzer of energy, with the polymerization of the described Resins, epoxy of catalysis.

17. coated abrasive article as claimed in claim 3, pre-glued backing as claimed in claim 4, or the described composition of claim 6 is characterized in that described vinyl-vinyl acetate copolymer contains the 20-99% weight vinyl-acetic ester of having an appointment.

18. coated abrasive article as claimed in claim 3, or pre-glued backing as claimed in claim 4, it is characterized in that described binder precursor contains the 50-94% weight ring epoxy resins of having an appointment, about 5-50% weight vinyl-vinyl acetate copolymer and about 0.1-15% weight polyfunctional acrylic ester component, described vinyl-vinyl acetate copolymer contains the 40-90% weight vinyl-acetic ester of having an appointment.

19. composition as claimed in claim 6 is characterized in that it is solution mixture or molten mixture.

20. composition as claimed in claim 6, the content that it is characterized in that described Resins, epoxy is about 2-98% weight, the content of described ethylene-vinyl acetate copolymer resin is about 1-90% weight, described polyfunctional acrylic ester components contents is about 0.1-20% weight, and weight percentage is pressed the resin total content and calculated.

21. composition as claimed in claim 6, the content that it is characterized in that described Resins, epoxy is about 70-92% weight, the content of described ethylene-vinyl acetate copolymer resin is about 5-30% weight, and it contains and accounts for the about 40-95% weight of multipolymer weight vinyl-acetic ester, described polyfunctional acrylic ester components contents is about 3-15% weight, weight percentage is pressed the resin total content and is calculated, curing agent for epoxy resin is the photolytic activity solidifying agent, and the solidifying agent of polyfunctional acrylic ester component is a light trigger.